CN1849345B - Stabilized fluoropolymer and method for producing same - Google Patents
Stabilized fluoropolymer and method for producing same Download PDFInfo
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- CN1849345B CN1849345B CN2004800261078A CN200480026107A CN1849345B CN 1849345 B CN1849345 B CN 1849345B CN 2004800261078 A CN2004800261078 A CN 2004800261078A CN 200480026107 A CN200480026107 A CN 200480026107A CN 1849345 B CN1849345 B CN 1849345B
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- fluoropolymer
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- stable
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- sulfonic acid
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 255
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 253
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 107
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 53
- 238000004334 fluoridation Methods 0.000 claims description 48
- 229910052731 fluorine Inorganic materials 0.000 claims description 43
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000012025 fluorinating agent Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000013076 target substance Substances 0.000 abstract 2
- 238000003682 fluorination reaction Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 45
- 229920000867 polyelectrolyte Polymers 0.000 description 39
- 239000000446 fuel Substances 0.000 description 38
- 238000006116 polymerization reaction Methods 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000126 substance Substances 0.000 description 34
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 34
- 210000004027 cell Anatomy 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000007789 gas Substances 0.000 description 27
- 238000000465 moulding Methods 0.000 description 24
- 239000013543 active substance Substances 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 238000005342 ion exchange Methods 0.000 description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001192 hot extrusion Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000004382 potting Methods 0.000 description 6
- 230000000452 restraining effect Effects 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 150000003460 sulfonic acids Chemical class 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 239000006188 syrup Substances 0.000 description 6
- 235000020357 syrup Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000004742 high temperature nuclear magnetic resonance Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000000207 volumetry Methods 0.000 description 4
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 210000000170 cell membrane Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910000753 refractory alloy Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000013518 transcription Methods 0.000 description 2
- 230000035897 transcription Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- PACOTQGTEZMTOT-UHFFFAOYSA-N bis(ethenyl) carbonate Chemical compound C=COC(=O)OC=C PACOTQGTEZMTOT-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000032677 cell aging Effects 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005443 coulometric titration Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a method for producing a stabilized fluoropolymer which comprises producing the stabilized fluoropolymer by subjecting a treatment target substance containing a sulfonic-acid-derived-group-containing fluoropolymer to a fluorination treatment, wherein the sulfonic-acid-derived-group-containing fluoropolymer is a fluoropolymer containing -SO 3 M (in which M representsH, NR 1 R 2 R 3 R 4 or M 1 1/L ; R 1 , R 2 , R 3 and R 4 are the same or different and each represents H or an alkyl group containing 1 to 4 carbon atoms; and M 1 represents an L-valent metal), and the treatment target substance has a moisture content of not higher than 500 ppm by mass.
Description
Technical field
Stable fluoropolymer that the present invention relates to the manufacture method of stable fluoropolymer, obtains by this method and the polyelectrolyte membrane that contains the hydrolyzate of this stable fluoropolymer.
Background technology
For with tetrafluoroethylene and having-SO
2The fluoropolymer that contains the sulfonic acid deriveding group that the perfluoroalkyl vinyl ether copolymerization of F obtains has been known-SO
2The hydrolyzate that F obtains through hydrolysis is used as the purposes of the membrane materials for electrolyte of fuel cell, chemical sensor etc.
For this hydrolyzate that contains the fluoropolymer of sulfonic acid deriveding group, for example reported that when acting as a fuel electrolyte for batteries film life-time service the water that takes place to flow out from fuel cell aging back contains the problem of HF.
Have report to point out, this problem is by following stabilization treatment can improve (for example, with reference to patent documentation 1).Promptly under 20 ℃～300 ℃, make the fluoropolymer that contains the sulfonic acid deriveding group of the compound contact solid state of generation fluoro free radical such as fluorine gas, make the unstable group of polymer chain end at least 40% be converted to stable group thus, improve this problem with this.
The fluoropolymer that particularly ought contain the sulfonic acid deriveding group is under the situation about obtaining by letex polymerization, and stabilization treatment in the past exists unstable group insufficient to the turnover ratio of stablizing the group conversion, and the problem painted, foaming that produces is arranged during melt molding.
Patent documentation 1: special public clear 46-23245 communique
Summary of the invention
In view of above-mentioned present situation, the fuel cell membranes of the high-durability of stable fluoropolymer that the object of the present invention is to provide the method that will contain the fluoropolymer sufficient stabilization of sulfonic acid deriveding group, obtains by this method and the hydrolyzate that contains this stable fluoropolymer.
In the manufacture method of stable fluoropolymer of the present invention, by being carried out fluoridation, the process object thing that contains the fluoropolymer with sulfonic acid deriveding group makes stable fluoropolymer, it is characterized in that the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is to have-SO
3(M represents H, NR to M
1R
2R
3R
4Or M
1 1/L, R
1, R
2, R
3And R
4Can be identical or different, expression H or carbonatoms are 1～4 alkyl, M
1The metal of expression L valency) fluoropolymer, in the above-mentioned process object thing, in mass, moisture is smaller or equal to 500ppm.
The present invention relates to stable fluoropolymer, it is characterized in that, it is that manufacture method by the fluoropolymer of aforementioned stable obtains.
The present invention relates to stable fluoropolymer, it is the stable fluoropolymer that obtains through following polymerization, described polymerization is the perhalogeno vinyl ether that contains sour deriveding group of following general formula (II) expression and the polymerization of tetrafluoroethylene, it is characterized in that, fluoropolymer for aforementioned stable, in IR (infrared spectroscopic analysis) measures, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] smaller or equal to 0.05;
CF
2＝CF-O-(CFY
2)
m-A (II)
In the general formula (II), Y
2Expression F, Cl, Br or I, m represents 1～5 integer, when m is 2～5 integer, m Y
2Can be identical or different, A represents-SO
2X or-COZ, X represent F, Cl, Br, I or-NR
5R
6, Z represents-NR
7R
8Or-OR
9, R
5, R
6, R
7And R
8Can be identical or different, expression H, alkali metal, alkyl or contain the group of alkylsulfonyl, R
9The expression carbonatoms is 1～4 alkyl.
The present invention relates to stable fluoropolymer, it is the stable fluoropolymer that obtains through the perhalogeno vinyl ether that contains sour deriveding group of above-mentioned general formula (II) expression and the polymerization of tetrafluoroethylene, it is characterized in that, hydrolyzate for the fluoropolymer of aforementioned stable, in the carbon atom of the main chain of per 100,000 formation said hydrolyzed things, the main chain end-CF of existence
3The number of group [X] is more than or equal to 10; Concrete number [X] is to use the main chain end-CF of said hydrolyzed thing
3The integrated intensity of group, the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-integrated intensity and calculate according to the ion-exchange equivalent weight Ew value that volumetry is tried to achieve; Main chain end-the CF of described hydrolyzate
3The integrated intensity of group and the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-integrated intensity be by make the swelling of said hydrolyzed thing in relative permittivity more than or equal to 5.0 oxygen-containing hydrocarbon compounds in, carry out
19The F solid-state nuclear magnetic resonance is measured and is tried to achieve.
The present invention relates to polyelectrolyte membrane, it contains the hydrolyzate of the fluoropolymer of aforementioned stable.
The present invention relates to the active substance fixed body, it is characterized in that, it contains the hydrolyzate and the active substance of the fluoropolymer of aforementioned stable.
The present invention relates to film/assembly of electrode, it is the film/assembly of electrode that is formed by polyelectrolyte membrane and electrode, it is characterized in that, it is the film/assembly of electrode that satisfies at least 1 condition that is selected from the group that is formed by following condition (1) and condition (2); Described condition (1) is: above-mentioned polyelectrolyte membrane is a polyelectrolyte membrane of the present invention; Described condition (2) is: above-mentioned electrode is above-mentioned active substance fixed body.
The present invention relates to solid macromolecular electrolyte type fuel cell, it is characterized in that, it has above-mentioned film/assembly of electrode.
Description of drawings
[Fig. 1] carries out the stable fluoropolymer G that obtains with embodiment 5
19The F solid-state nuclear magnetic resonance is measured and the NMR figure (longitudinal axis is 13 times of Fig. 2) that obtains.
[Fig. 2] carries out the stable fluoropolymer G that obtains with embodiment 5
19The F solid-state nuclear magnetic resonance is measured and the NMR figure that obtains.
Embodiment
Hereinafter the present invention is described in detail.
In the manufacture method of stable fluoropolymer of the present invention, the process object thing that contains the fluoropolymer with sulfonic acid deriveding group is carried out fluoridation make stable fluoropolymer.
The above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is to have-SO
3(M represents H, NR to M
1R
2R
3R
4Or M
1 1/L) fluoropolymer.
Above-mentioned NR
1R
2R
3R
4In R
1, R
2, R
3And R
4Can be identical or different, expression H or carbonatoms are 1～4 alkyl.
As above-mentioned carbonatoms is 1～4 alkyl, though do not limit especially, is preferably straight chained alkyl, more preferably methyl.
Above-mentioned M
1The metal of expression L valency.The metal of above-mentioned L valency is the metal that belongs to periodictable the 1st row, the 2nd row, the 4th row, the 8th row, the 11st row, the 12nd row or the 13rd row.
As the metal of above-mentioned L valency, do not limit especially, for example,, can enumerate Li, Na, K, Cs etc. as the 1st row of periodictable; As the 2nd row of periodictable, can enumerate Mg, Ca etc.; As the 4th row of periodictable, can enumerate Zr etc.; As the 8th row of periodictable, can enumerate Fe etc.; As the 11st row of periodictable, can enumerate Cu, Ag etc., as the 12nd row of periodictable, can enumerate Zn etc., as the 13rd row of periodictable, can enumerate Al etc.
The fluoropolymer that contains the sulfonic acid deriveding group is except above-mentioned-SO
3M can also further have-SO
2X and/or-COZ (X represent F, Cl, Br, I or-NR
5R
6Z represents-NR
7R
8Or-OR
9R
5, R
6, R
7Or R
8Can be identical or different, expression H, alkali metal, alkyl or contain the group of alkylsulfonyl.R
9The expression carbonatoms is 1～4 alkyl).
Above-mentioned-SO
2X among the X is preferably F, Cl or Br, more preferably F.
Z among above-mentioned-COZ is preferably-OR
9
As above-mentioned alkali metal, do not limit especially, for example can enumerate Li, Na, K, Cs etc.
As abovementioned alkyl, do not limit especially, for example can enumerate, carbonatomss such as methyl, ethyl are 1～4 alkyl etc.Abovementioned alkyl can have halogen atom to replace.
The above-mentioned group that contains sulfonyl group is the fluoroalkyl that contains with sulfonyl group, for example can enumerate, and fluorine-containing alkyl sulfonyl group etc., it can have substituted radical endways,, for example can enumerate-SO as above-mentioned fluorine-containing alkyl sulfonyl group
2R
f 1Z
1(R
f 1Represent fluorine-containing alkylidene group, Z
1The expression organic group) etc.
As above-mentioned organic group, for example can enumerate-SO
2F can be as-SO
2(NR
5SO
2R
f 1SO
2)
kNR
5SO
2-(k represents the integer more than or equal to 1, R
f 1Represent fluorine-containing alkylidene group) like that ad infinitum prolong down, for example, can be-SO
2(NR
5SO
2R
f 1SO
2)
kNR
5SO
2(k represents 1～100 integer to F.R
5And R
f 1Same as described above).When using with fuel cell applications and since hydrolysis produce-COOH has problem aspect stable, so preferably do not contain-COZ.
The above-mentioned fluoropolymer that contains the sulfonic acid deriveding group further can also have at the polymer chain end-COOH.
For example, the above-mentioned-COOH that derives from the molecular structure of polymerization starter is introduced the above-mentioned main chain end that contains the fluoropolymer of sulfonic acid deriveding group.
For example, when using peroxide carbonic diester etc. as polymerization starter, above-mentioned-COOH is formed at the above-mentioned main chain end that contains the fluoropolymer of sulfonic acid deriveding group.If the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group obtains by letex polymerization, have-COOH at the polymer chain end usually.
In addition, when using the perfluoroalkyl dicarboxylic acid in non-aqueous system, to carry out polymerization as polymerization starter, though the part of polymer chain end becomes perfluoroalkyl, formation-COOH and-COF usually.This is by the β-cracking of perhalogeno vinyl ether (β-scission) produce.
The above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is preferably by the perhalogeno vinyl ether that contains sour deriveding group and 2 yuan of can form with the above-mentioned monomer that contains the perhalogeno vinyl ether copolymerization of sour deriveding group or polybasic multipolymer more.
The above-mentioned perhalogeno vinyl ether that contains sour deriveding group is preferably the compound that following general formula (I) is represented;
CF
2＝CF-O-(CF
2CFY
1-O)
n-(CFY
2)
m-A (I)
Y in the above-mentioned general formula (I)
1Expression F, Cl, Br, I or perfluoroalkyl wherein, are preferably perfluoroalkyl, and more preferably carbonatoms is 1～3 perfluoroalkyl, more preferably-and CF
3
N in the above-mentioned general formula (I) represents 0～3 integer, n Y
1Can be identical or different.Said n is preferably 0 or 1, and more preferably 0.
Y in the above-mentioned general formula (I)
2Expression F, Cl, Br or I wherein, are preferably F.
M in the above-mentioned general formula (I) represents 1～5 integer.When m is 2～5 integer, m Y
2Can be identical or different.Above-mentioned m is preferably 2.
Above-mentioned general formula (I), preferred Y
2Be F, m is 2.More preferably Y
2For F, m are 2, n is 0.
A in the above-mentioned general formula (I) represents that sour deriveding group is-SO
2X or-COZ (X is identical with above-mentioned definition with Z).
Above-mentioned-the SO that has as the above-mentioned fluoropolymer selectivity that contains the sulfonic acid deriveding group
2X and/or-COZ, can introduce above-mentioned group by the perhalogeno vinyl ether that contains sour deriveding group of the above-mentioned general formula of polymerization (I) expression.
The above-mentioned compound that contains the more preferably following general formula of perhalogeno vinyl ether (II) expression of sour deriveding group;
CF
2＝CF-O-(CFY
2)
m-A (II)
In the general formula (II), Y
2, the Y in m and A and the above-mentioned general formula (I)
2, m is identical with A.
The above-mentioned perhalogeno vinyl ether that contains sour deriveding group can use a kind or at least 2 kinds of uses of combination.
Can with the above-mentioned monomer that contains the perhalogeno vinyl ether copolymerization of sour deriveding group, be preferably other vinyl ether and the vinyl-type monomer except the above-mentioned perhalogeno vinyl ether that contains sour deriveding group.As above-mentioned can with the monomer of the perhalogeno vinyl ether copolymerization that contains sour deriveding group, corresponding to purpose, can from the group that above-mentioned " vinyl ether and the vinyl-type monomer of other except the perhalogeno vinyl ether that contains sour deriveding group " forms, select at least a kind.
Above-mentioned vinyl-type monomer is not have ether oxygen but monomer with vinyl, and in the above-mentioned vinyl, part or all of hydrogen atom can be replaced by fluorine atom.
As above-mentioned vinyl-type monomer, can enumerate vinyl halides type monomer that for example following general formula represents,
CF
2＝CF-Rf
2
(in the above-mentioned general formula, Rf
2Expression F, Cl or carbonatoms are 1～9 a straight chain shape or a catenate fluoro-alkyl)
The hydrogeneous fluorinated ethylene type monomer that following general formula is represented etc.;
CHY
3＝CFY
4
(in the above-mentioned general formula, Y
3Expression H or F, Y
4Expression H, F, Cl or carbonatoms are 1～9 a straight chain shape or a catenate fluoroalkyl)
Above-mentioned vinyl-type monomer is preferably and is selected from by with CF
2=CF
2, CH
2=CF
2, CF
2=CFCl, CF
2=CFH, CH
2=CFH and CF
2=CFCF
3At least a kind of monomer of the group that the fluorinated ethylene base ether of expression forms, wherein, perhalogeno vinyl-type monomer more preferably, more preferably perfluoro-ethylene type monomer is preferably tetrafluoroethylene especially.
As above-mentioned vinyl-type monomer, can use a kind or at least 2 kinds.
As other the vinyl ether except the above-mentioned perhalogeno vinyl ether that contains sour deriveding group, only otherwise containing above-mentioned sour deriveding group get final product, qualification especially for example can be enumerated, the perfluoroalkyl vinyl ether that following general formula is represented,
CF
2＝CF-O-Rf
3
(in the above-mentioned general formula, Rf
3The expression carbonatoms is that 1～9 fluoro-alkyl or carbonatoms are 1～9 fluorochemical polyether base)
The hydrogeneous vinyl ether that following general formula is represented etc.;
CHY
5＝CF-O-Rf
4
(in the above-mentioned general formula, Y
5Expression H or F, Rf
4The expression carbonatoms is a straight chain shape or the catenate fluoro-alkyl that 1～9 selectivity has ether oxygen)
As above-mentioned other vinyl ether, can use a kind or at least 2 kinds.
As the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, form though preferably will a kind contain the perhalogeno vinyl ether of sour deriveding group and at least a kind of vinyl-type monomer copolymerization at least 2 yuan or polybasic multipolymer more, more preferably with a kind of perhalogeno vinyl ether that contains sour deriveding group and a kind of vinyl-type monomer copolymerization and 2 membered copolymers that obtain, but according to expectation, can be except containing the perhalogeno vinyl ether and the vinyl-type monomer of sour deriveding group, also copolymerization except the perhalogeno vinyl ether that contains sour deriveding group other vinyl ether and the multipolymer that obtains.
The vinyl ether unit of other that the vinyl-type monomer unit that the perhalogeno vinyl ether unit that contains sour deriveding group that the fluoropolymer that contains the sulfonic acid deriveding group among the present invention is preferably wherein formed by the above-mentioned perfluoroalkyl vinyl ether that contains sour deriveding group is 5 moles of %～40 mole %, formed by above-mentioned vinyl-type monomer is 60 moles of %～95 mole %, formed by above-mentioned other vinyl ether is 0 mole of %～5 mole %.
Be limited to 7 moles of % under the above-mentioned perhalogeno vinyl ether unit that contains sour deriveding group is preferred, further preferably be limited to 10 moles of % down, be limited to 35 moles of % on preferred, further be limited to 30 moles of % on preferably.
Be limited to 65 moles of % under above-mentioned vinyl-type monomer unit is preferred, further preferably be limited to 70 moles of % down, be limited to 90 moles of % on preferred, further be limited to 87 moles of % on preferably.
Be limited to 4 moles of % on above-mentioned other vinyl ether unit is preferred, be limited to 3 moles of % on further preferred.
Above-mentioned " vinyl-type monomer unit " is the part on the molecular structure of the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, refers to the part of the molecular structure that derives from vinyl-type monomer.For example, tetrafluoroethylene units refers to and derives from tetrafluoroethylene [CF
2=CF
2] part [CF
2-CF
2-].
Above-mentioned " the perhalogeno vinyl ether unit that contains sour deriveding group " is the part on the molecular structure of the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, refers to the part of the molecular structure that derives from the perhalogeno vinyl ether that contains sour deriveding group.
Above-mentioned " other vinyl ether unit " is the part on the molecular structure of the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, refers to derive from above-mentioned other the part of molecular structure of vinyl ether.
In this specification sheets, above-mentioned perhalogeno vinyl ether unit, vinyl-type monomer unit and the unitary content of other vinyl ether that contains sour deriveding group is respectively with the value of whole monomeric units as 100% mole.
Above-mentioned " all monomeric unit " is the summation of the part that formed by monomer on the molecular structure of the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group.Therefore, forming the monomer of above-mentioned " all monomeric units ", is to form the above-mentioned monomeric summation that contains the fluoropolymer of sulfonic acid deriveding group.
In this specification sheets, the content of above-mentioned " the perhalogeno vinyl ether unit that contains sour deriveding group " (mole %), be in the monomeric mole number of the whole monomeric units in forming the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, form the unitary shared ratio of mole number that contains the perhalogeno vinyl ether of sour deriveding group of perhalogeno vinyl ether that contains sour deriveding group.Similarly, the content (mole %) of the content of above-mentioned " vinyl-type monomer unit " (mole %) and above-mentioned " other vinyl ether unit " is the ratio as the monomeric mole number in its source.These each unitary content are by using high temperature
19F-nuclear magnetic resonance measuring device (the system JNM-FX100 of NEC society of Japan type) is solvent-freely measured the value that obtains under 300 ℃.Hereinafter abbreviate this mensuration as high temperature NMR.
As the above-mentioned polymkeric substance method that contains the fluoropolymer of sulfonic acid deriveding group, it for example can be any means in the known method in the past such as solution polymerization, suspension polymerization, letex polymerization, but consider the performance best effect, the manufacture method of stable fluoropolymer of the present invention is preferably letex polymerization.
For example, if the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is to have-SO
2The monomer of F carries out that letex polymerization obtains, then in polymerization process, and-SO
2The few part of F is transformed to-SO
3H.Should-SO
3H exists
+NR
1R
2R
3R
4Or M
1L+Existence under, can easily be transformed to-SO
3NR
1R
2R
3R
4Or-SO
3M
1 1/L(above-mentioned R
1, R
2, R
3, R
4And M
1Identical with above-mentioned definition).
Have-SO as above-mentioned
2The monomer of F does not limit especially, for example can enumerate, and the A in the above-mentioned general formula (I) is-SO
2The perhalogeno vinyl ether that contains sour deriveding group of F etc.And, among the present invention contain the sulfonic acid deriveding group fluoropolymer had-SO
3M (M is identical with above-mentioned definition), be not limited to above-mentioned be used for letex polymerization monomer had-SO
2F deutero-group for example, can be the group of introducing by known method.
In the manufacture method of stable fluoropolymer of the present invention, the above-mentioned process object thing that contains the fluoropolymer with sulfonic acid deriveding group is carried out fluoridation.
In this specification sheets, above-mentioned " process object thing " is the object that carries out above-mentioned fluoridation.
Above-mentioned process object thing can be the arbitrary form such as membranaceous that resin-oatmeal powder, particulate state, moulding obtain.Consider and carry out fluoridation described later fully, above-mentioned process object thing is preferably the resin-oatmeal powder, considers operability, the industrial particulate state that is preferably.
When carrying out fluoridation by existing method, the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group has fluoridizes inadequate problem.It is believed that and fluoridize inadequate the reasons are as follows, even solid forms such as that the promptly above-mentioned fluoropolymer that contains the sulfonic acid deriveding group through drying treatment, is modulated into is Powdered, particulate state, formed body, usually, also because-SO
3The M water absorbability is high and directly absorb airborne moisture.Above-mentioned-SO
3The high-hygroscopicity of M is more than such as-COOH, the salt of-COOH ,-COZ ,-(Z is identical with above-mentioned definition with X) other functional groups such as SOX are big.Though the humidity of moisture content and existing atmosphere gas etc. are relevant, because should-SO
3The high-hygroscopicity of M is in the solid of main component with the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group in fact, and moisture surpasses 500ppm usually in mass.High containing like this has the solid of the fluoropolymer of above-mentioned sulfonic acid deriveding group for water ratio, if carry out fluoridation by existing method, then in the reaction of following reaction formula (A) expression, consume fluorine source (F), thereby hindered fluoridizing of the fluoropolymer that contains the sulfonic acid deriveding group;
2H
2O+4(F)→4HF+O
2 (A)
In the manufacture method of stable fluoropolymer of the present invention, in the process object thing, in mass, moisture is smaller or equal to 500ppm.If surpass 500ppm, then owing to hindered fluoridizing of the fluoropolymer that contains the sulfonic acid deriveding group, this is unfavorable.Be limited to 450ppm on preferred, be limited to 350ppm on preferred.As long as the moisture in the above-mentioned process object thing is then considered economy, productivity in above-mentioned scope, for example lower limit can be 0.01ppm.
Water content in the above-mentioned process object thing, the value that is to use the karl Fischer titration measuring to obtain.
In the manufacture method of stable fluoropolymer of the present invention, suppress obstruction reaction by under the condition of water content in above-mentioned scope of process object thing, carrying out fluoridation, fully the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is fluoridized such as the fluoridation of above-mentioned reaction (A).
As making moisture in the process object thing in the method for above-mentioned scope, do not limit especially, for example, can use existing known drying means: for example as required, after centrifuge dehydration, under 80 ℃～130 ℃, heated 2 hours～50 hours, change temperature therebetween as required interimly, and reduce pressure as required, heat, carry out the exsiccant method with this; In exhaust pass forcing machine, make the fusion of process object thing, slough volatile component, carry out the exsiccant method with this from venting hole.Consider and to decompose a part-SO
3M is so preferably use the latter's method.
Because the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group has the functional group of high-hygroscopicity, for from the above-mentioned operation that is dried to fluoridation described later, preferably carries out closure or carries out these operations as early as possible.
Fluoridation in the manufacture method of stable fluoropolymer of the present invention is to use the fluorine source to carry out.
Above-mentioned fluorine source is preferably selected from by F
2, SF
4, IF
5, NF
3, PF
5, ClF and ClF
3At least a kind of material of the group that forms, more preferably F
2
The preferred gaseous fluorinating agent that contains above-mentioned fluorine source that uses carries out above-mentioned fluoridation.At this moment, above-mentioned fluorine source is preferably greater than the 1 volume % that equals above-mentioned gaseous fluorinating agent.Be limited to 10 capacity % under preferred.
Above-mentioned gaseous fluorinating agent contains above-mentioned fluorine source and is inert gasses to fluoridizing.
Be inert gasses as above-mentioned for fluoridizing, do not limit especially, can enumerate for example nitrogen, argon gas etc.
Preferably under less than the temperature of the fusing point of fluoropolymer, implement above-mentioned fluoridation, usually, under smaller or equal to 250 ℃ temperature, more preferably under room temperature～150 ℃, carry out above-mentioned fluoridation.
For above-mentioned fluoridation, can carry out any one operation of continous way, batch type.
In addition, can leave standstill the formula reactor from template reactor, cartridge type reactor etc.; Reactor with agitating wing; Containers such as rotary kiln, the tapered reactor of W, V-type muller rotation (reverse) formula reactor; The oscillatory type reactor; The device that uses in the above-mentioned fluoridation of suitable selection in the various flowing bed reactors such as stirring thermopnore.
In above-mentioned fluoridation, even in order to keep temperature of reaction, can use for fluorocarbon class etc. the fluorine source is the inert solvent.In addition, when the process object thing is resin-oatmeal powder, particulate state, consider that easy maintenance temperature of reaction is even, preferably use rotary reactor of container or oscillatory type reactor to carry out fluoridation.
Above-mentioned fluoridation is following processing: fluoridize by the unstable group of the easy pyrolysated that the fluoropolymer that contains the sulfonic acid deriveding group before the fluoridation is had, should easy pyrolysated instability group be transformed into and be difficult to pyrolysated and stablize group.
Above-mentioned fluoridation preferably with above-mentioned contain the sulfonic acid deriveding group fluoropolymer had-CF
2SO
3M (M is identical with above-mentioned definition) is transformed into-CF
2H ,-CF
3Deng, further as required, respectively with the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group chain end had-COOH is transformed to-CF
3, general-SO
2NH
2Be transformed to-SO
2F.
For above-mentioned fluoridation,, when using the melt molding of the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group, can prevent-SO by these conversion
3Unstable group thermolysis such as M and painted, prevent-unstable group such as COOH decomposes and foams.
By above-mentioned fluoridation, can remove the impurities such as lower molecular weight body, unreacted monomer, by product such as oligopolymer that contain in the process object thing.
And, by fluoridation, with above-mentioned contain the sulfonic acid deriveding group fluoropolymer had-SO
3M (M is identical with above-mentioned definition) be transformed to do not have ion-exchange capacity-CF
2H ,-CF
3Deng, if above-mentioned-SO
3M is that above-mentioned monomer has-SO
2F obtains by the letex polymerization conversion, and this moment is because from-SO
2F transforms to-SO
3Even the interconversion rate of M is a trace extremely, so when being used for shaping membrane etc. on the ion-exchange purposes after the above-mentioned fluoridation, also can keeping ion-exchange equivalent weight [Ew] and it is significantly increased.
In the manufacture method of stable fluoropolymer of the present invention, make stable fluoropolymer by carrying out above-mentioned fluoridation.
In this specification sheets, above-mentioned " stable fluoropolymer " be by the fluoropolymer that contains the sulfonic acid deriveding group by carrying out the fluoropolymer that above-mentioned fluoridation obtains, be that the above-mentioned fluoropolymer that contains the sulfonic acid deriveding group is had-COOH, CF
2SO
3M ,-SO
2NH
2Be transformed to-CF etc. the unstable group of easy pyrolysated
2H ,-CF
3,-SO
2F etc. are difficult to the stable fluoropolymer that pyrolysated is stablized group.
After the above-mentioned fluoridation, volatile component such as the fluoropolymer of aforementioned stable and HF is also deposited, so preferably remove these volatile components.
The preferred forcing machine with devolatilization constituent structure that uses carries out removing of above-mentioned volatile component, more preferably uses the exhaust pass forcing machine with at least 1 venting hole.
As the process object thing that carries out fluoridation; though above point out to be preferably the resin-oatmeal powder; but when being to use toner as the process object thing; for the process object thing, preferably carry out fluoridation after, fusion is mixed and is removed above-mentioned volatile component in exhaust pass forcing machine; then carry out granulating; more preferably in above-mentioned exhaust pass forcing machine, carry out fluoridation, then, in identical forcing machine, remove above-mentioned volatile component and carry out granulating.
Even the process object thing is membranaceous, utilize above-mentioned fluoridation also can similarly carry out stabilization.
This membranous body when the dielectric film, is carried out not being subjected to after the stabilization treatment infringement of big heat, and the unstable group that produces because of the polymkeric substance chain break from this aspect, does not preferably carry out above-mentioned fluoridation to membranous body.
Above-mentioned fluoridation when being membranaceous as above-mentioned process object thing is preferably as follows enforcement.Use particle, for example utilize and in above-mentioned exhaust pass forcing machine, make the fusion of process object thing and come the particle of moulding from the method for venting hole devolatilization composition, melt extrude the system film then, after this, the reaction unit that uses the cartridge type reactor or have a reeling machine is implemented fluoridation.
Implement under the situation of drying treatment before stating the fluoridation of various reaction units in the use, preferably reduce pressure or circulate dry gas.
In addition, the fluoropolymer that contains the sulfonic acid deriveding group in the above-mentioned process object thing has-and COF is during as unstable group, in order to make it stable, need higher temperature, so can be in advance by hydrolysis etc. it is transformed to-COOH after, adjust water content and make it implement fluoridation smaller or equal to 500ppm.
Among the present invention, the fluoropolymer of aforementioned stable be the polymer chain end that will before above-mentioned fluoridation, have usually-COOH is transformed to-CF by above-mentioned fluoridation
2H ,-CF
3Stable fluoropolymer etc. stable group.In the manufacture method of stable fluoropolymer of the present invention, this interconversion rate is high, in infrared spectroscopic analysis [IR] is measured, can make the peak [x] that derives from carboxyl and derives from-CF
2The strength ratio [x/y] at peak [y] smaller or equal to 0.05.Be limited to 0.04 on above-mentioned strength ratio [x/y] preferred, be limited to 0.03 on preferred.
In addition, the stable fluoropolymer (hereinafter being sometimes referred to as " stable fluoropolymer (A) ") that obtains of the manufacture method of the fluoropolymer by aforementioned stable also is one of the present invention.
Among the present invention, stable fluoropolymer preferably has the feature of stable fluoropolymer (A) and has the feature of stable fluoropolymer (B) described later, perhaps have the feature of stable fluoropolymer (A) and have the feature of stable fluoropolymer (C) described later, perhaps have stable fluoropolymer (A) feature, have the feature of stable fluoropolymer (B) described later and have the feature of stable fluoropolymer (C) described later.
Stable fluoropolymer of the present invention (hereinafter being sometimes referred to as fluoropolymer (B)) is through above-mentioned general formula (II) (Y
2, m is identical with above-mentioned definition with A) the stable fluoropolymer that obtains of the perhalogeno vinyl ether that contains sour deriveding group of expression and the polymerization of tetrafluoroethylene, fluoropolymer for aforementioned stable, in IR measures, derive from the peak [x] of carboxyl and derive from-CF
2-the strength ratio [x/y] at peak [y] smaller or equal to 0.05.
Above-mentionedly contain the perhalogeno vinyl ether of sour deriveding group and the polymerization of tetrafluoroethylene is preferably letex polymerization.
In the fluoropolymer of aforementioned stable (B), above-mentioned carboxyl [COOH] mainly forms with the form of polymer chain end group, and above-mentioned-CF
2-mainly be present in main polymer chain.
In the fluoropolymer of aforementioned stable (B), be limited to 0.04 on above-mentioned strength ratio [x/y] is preferred, be limited to 0.03 on preferred.
As long as the fluoropolymer (B) of aforementioned stable has the strength ratio [x/y] in the above-mentioned scope, do not limit especially for its manufacture method, the manufacture method of the stable fluoropolymer of the application of the invention can easily obtain the fluoropolymer (B) of aforementioned stable.
The manufacture method of the stable fluoropolymer by the invention described above, can obtain the fluoropolymer (B) of aforementioned stable effectively, but it must be the stable fluoropolymer that the manufacture method of the stable fluoropolymer by the invention described above obtains that the fluoropolymer of aforementioned stable (B) is not limited to, in this, its notion with the fluoropolymer (A) of aforementioned stable is different.
In this specification sheets, not additional (A), (B) and (C) described later, when only claiming " stable fluoropolymer ", in stable fluoropolymer (A), stable fluoropolymer (B) and the stable fluoropolymer (C) described later which do not distinguish is, be upperseat concept, can comprise stable fluoropolymer (A), stable fluoropolymer (B) and/or stable fluoropolymer described later (C).
For the fluoropolymer of aforementioned stable, in infrared spectroscopic analysis [IR] is measured, because above-mentioned strength ratio [x/y] is in above-mentioned scope, so be difficult for producing foaming during melt molding.
Among the present invention, above-mentioned strength ratio [x/y] is that each peak intensity that obtains from using infrared spectrophotometer to measure is calculated.
The above-mentioned peak [x] that derives from carboxyl is at 1776cm
-1Near the association body that derives from carboxyl that observes absorption peak strength and at 1807cm
-1Near the absorption peak strength that derives from non-association body that observes and.
Above-mentioned deriving from-CF
2-peak [y] be to derive from-CF
2-the absorption peak of harmonic wave.
The fluoropolymer of aforementioned stable, the amount of preferred alkylsulfonyl is smaller or equal to 200ppm.Be limited to 50ppm on preferred.
The fluoropolymer of aforementioned stable, the amount of preferred carboxyl is smaller or equal to 100ppm.Be limited to 30ppm on preferred.
In this specification sheets; the amount of above-mentioned alkylsulfonyl and the amount of carboxyl are the following values that obtains: stable fluoropolymer is carried out 20 minutes the hot extrusion that adds under 270 ℃, 10MPa; making thickness is the mensuration film of 150 μ m～200 μ m; use the FT-IR optical splitter to measure spectrum, the value that obtains by following process.
At first, by under 150 ℃, carrying out fluoridation 20 hours, make in addition in advance the unstable group standard model of stabilization fully, carry out stdn with the absorption peak of C-F harmonic wave and derive its IR collection of illustrative plates and measure poor spectrogram with the IR collection of illustrative plates of film, in the poor collection of illustrative plates that obtains, read in 1056cm
-1Near observe the absorption peak that derives from sulfonic acid group, at 1776cm
-1Near the absorption peak and the 1807cm of the association body that derives from carboxyl that observes
-1Near the intensity of the absorption peak that derives from non-association body that observes, and carry out the stdn peak intensity Abs that is absorbed with the peak intensity of C-F harmonic wave respectively.
Uptake factor ε (cm by the absorption peak of each functional group
3/ molcm), the proportion d (g/cm of sample
3) and the intensity of C-F harmonic wave be 1 o'clock sample thickness 1 (cm), use lambert beer's law (Abs=ε cl, c are concentration), calculate the amount of each functional group based on following formula:
Functional group (ppm)={ Abs * (molecular weight of each functional group) } * 10
11/ ε d1
In this specification sheets, the amount of above-mentioned carboxyl be the amount of association body of carboxyl and non-association body amount and.
In addition, stable fluoropolymer (hereinafter being sometimes referred to as " stable fluoropolymer (C) ") also is one aspect of the present invention, it is the stable fluoropolymer that the perhalogeno vinyl ether that contains sour deriveding group of above-mentioned general formula (II) expression and tetrafluoroethylene polymerization are obtained, it is characterized in that, hydrolyzate for the fluoropolymer of aforementioned stable, in the carbon atom of the main chain of per 100,000 formation said hydrolyzed things, the main chain end-CF of existence
3The number of group (X) is more than or equal to 10; Concrete number is to use the main chain end-CF of said hydrolyzed thing
3The integrated intensity of group, the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-integrated intensity and calculate according to the ion-exchange equivalent weight Ew value that volumetry is tried to achieve; Main chain end-the CF of described hydrolyzate
3The integrated intensity of group and the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-integrated intensity be by make the swelling of said hydrolyzed thing relative permittivity more than or equal to 5.0 oxygen-containing hydrocarbon compounds in, carry out
19The F solid-state nuclear magnetic resonance is measured and is tried to achieve.
Because above-mentioned main chain end-CF in the fluoropolymer (C) of aforementioned stable
3The number of group (X) is more than or equal to 10, so the main chain end group is by fully stable.
Above-mentioned main chain end-CF
3Be limited to 15 under the number of group (X) is preferred.
Above-mentioned main chain end-CF
3The number of group (X) is from main chain end-CF
3The integrated intensity of group, the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-the integrated intensity and the ion-exchange equivalent weight Ew value of the sample of trying to achieve according to volumetry calculate; Above-mentioned main chain end-CF
3The integrated intensity of group and the side chain adjacent with the ehter bond that goes out from the main chain branch-CF
2-integrated intensity be by carrying out
19The F solid-state nuclear magnetic resonance is measured and is tried to achieve.
Above-mentioned
19During the F solid-state nuclear magnetic resonance is measured, can use relative permittivity more than or equal to 5.0 oxygen-containing hydrocarbon compounds as the swelling solvent,, do not limit especially more than or equal to 5.0 oxygen-containing hydrocarbon compounds as relative permittivity, for example can enumerate N-methylacetamide etc.
Among the present invention, for use the swelling of N-methylacetamide fluoropolymer, be that 4.8kHz, mensuration frequency are 376.5MHz, chemical shift benchmark CF in MAS (Magic Angel Spinning) rotation number
3(77ppm), to measure temperature be under the condition of 473K to COOH, uses DSX400 (German Bruker Biospin society system) to carry out above-mentioned as determining instrument
19The F solid-state nuclear magnetic resonance is measured.Above-mentioned
19During the F solid-state nuclear magnetic resonance is measured, measure main chain end-CF by the signal at the peak of-79.7ppm
3The integrated intensity of group (A), by the signal at the peak of-76.4ppm measure the side chain adjacent with the ehter bond of the side chain that goes out from the main chain branch-CF
2-integrated intensity (B).
The ion-exchange equivalent weight Ew of the sample that can try to achieve by above-mentioned integrated intensity (A) and integrated intensity (B) and according to volumetry uses following formula (III) to calculate above-mentioned main chain end group-CF
3Number (X);
X＝100000/[{(B/A)×3/2}×{2×(Ew-178-50×m)/100}+2] (III)
Wherein, m defers to the m of above-mentioned general formula (II).
For the fluoropolymer (C) of aforementioned stable, in above-mentioned IR measures, preferably derive from the peak [x] of carboxyl and derive from-CF
2-the strength ratio [x/y] at peak [y] smaller or equal to 0.05.
For the fluoropolymer (C) of aforementioned stable, the preferred range of above-mentioned strength ratio [x/y] is identical with the scope of the middle related description of fluoropolymer (B) of aforementioned stable.
The fluoropolymer of aforementioned stable (C) then its manufacture method is not limited especially, but above-mentioned polymerization is preferably letex polymerization so long as obtain through the perhalogeno vinyl ether that contains sour deriveding group of above-mentioned general formula (II) expression and the polymerization of tetrafluoroethylene.
The manufacture method of stable fluoropolymer that can be by the invention described above obtains the fluoropolymer (C) of aforementioned stable effectively.It must be the stable fluoropolymer that the manufacture method of the stable fluoropolymer by the invention described above obtains that the fluoropolymer of aforementioned stable (C) is not limited to, and the notion with the fluoropolymer (A) of aforementioned stable is different in this.
By above-mentioned general formula (II) as can be known, the side chain of stable fluoropolymer (B) of the present invention and stable fluoropolymer (C) is short, is that the n in the above-mentioned general formula (I) is 0 such side chain.
According to the result of Fenton agent treated 1 described later, the inventor clearly finds the chemical stability excellence of short polymkeric substance of side chain, thereby has finished stable fluoropolymer (B) of the present invention and stable fluoropolymer (C).
Stable fluoropolymer of the present invention preferably according to JIS K7210, is that the melt index of measuring under 2.16 kilograms the condition is 0.1 gram/10 minutes～20 grams/10 minutes at 270 ℃, load.Melt index described herein [MI] also shows as melt turnover (MFR) sometimes.
For stable fluoropolymer of the present invention, if above-mentioned melt index [MI] during less than 0.1 (restrain/10 minutes), then has the trend that is difficult to melt molding, if above 20 (restraining/10 minutes), when then in fuel cell, using polyelectrolyte membrane, the easy variation of the weather resistance of battery.
Be limited to 0.5 (restraining/10 minutes) under above-mentioned MI preferred, be limited to 10 (restraining/10 minutes) on preferred.
In this specification sheets, MI is according to JIS K 7210,270 ℃, when the load that applies is 2.16 kilograms, the gram number of the weight of the polymkeric substance of extruding from the aperture of specific shape-size at per 10 minutes.
In addition, compared with unsettled fluoropolymer, even during melt molding, stable fluoropolymer of the present invention also is difficult to produce foaming.
Polyelectrolyte membrane of the present invention contains the hydrolyzate of the stable fluoropolymer of the invention described above.
Above-mentioned " hydrolyzate of stable fluoropolymer " is the fluoropolymer that stable fluoropolymer hydrolysis is obtained.
As the hydrolyzate of the fluoropolymer of aforementioned stable, for example can enumerate sulfonic acid type fluoropolymer, carboxylic acid type fluoropolymer etc.; Described sulfonic acid type fluoropolymer is by with stable sour deriveding group-SO that fluoropolymer had of the present invention
2The F alkalization is transformed to-SO
3Na ,-SO
3Alt form group groups such as K then are transformed to-SO by waiting with the acid effect
3H obtains; Described carboxylic acid type fluoropolymer is by general-COOCH
3Alkalization is transformed to-COONa ,-alt form group groups such as COOK, then by be transformed to acid effect etc.-COOH obtains.
Because polyelectrolyte membrane of the present invention contains the hydrolyzate of the fluoropolymer of aforementioned stable, when so it uses in fuel cell, chemical sensor etc. as membrane materials for electrolyte, even life-time service can not wear out yet, can also avoid simultaneously containing HF in the draining of fuel cell.
For example, m in the above-mentioned general formula (II) and/or A difference, different with the copolymerization ratio of TFE etc. can contain a kind or because the hydrolyzate of the fluoropolymer of at least 2 kinds the aforementioned stable that above-mentioned difference causes in the polyelectrolyte membrane of the present invention.
For polyelectrolyte membrane of the present invention, with respect to the above-mentioned polyelectrolyte membrane of 100 mass parts, the fluoride ion amount of stripping is smaller or equal to 11 * 10 by carrying out the Fenton agent treated
-4During mass parts, it is an ideal; Described Fenton agent treated is as follows: the film liquor ratio [b/a] with 3.2 restrains polyelectrolyte membrane with b, and to be immersed in the cationic initial stage concentration of iron (II) that a rises be 2ppm, and the initial stage concentration of hydrogen peroxide is in the aqueous hydrogen peroxide solution of 1 quality %, keeps 2 hours at 80 ℃.
If the fluoride ion amount is in above-mentioned scope, in the polyelectrolyte membrane of the present invention, the stable degree of stable fluoropolymer is enough high.
With respect to the above-mentioned polyelectrolyte membrane of 100 mass parts, the fluoride ion amount of stripping is more preferably less than and equals 8.0 * 10 by above-mentioned Fenton agent treated
-4Mass parts is further preferably smaller or equal to 5.0 * 10
-4Mass parts.With respect to the above-mentioned polyelectrolyte membrane of 100 mass parts, the fluoride ion amount by the stripping of above-mentioned Fenton agent treated is as long as in above-mentioned scope, even for example more than or equal to 1.0 * 10
-4Mass parts also allows industrial.
In this specification sheets, with ion chromatography (the system IC-2001 of east ソ one society of Japan, use the system TSKgel SuperIC-Anion of east ソ one society of Japan as the anion analysis pillar), measure above-mentioned fluoride ion amount according to the method for " Fenton agent treated 2 " described later.
The thickness of polyelectrolyte membrane preferred film of the present invention is 5 μ m～100 μ m.If less than 5 μ m, when then using it for fuel cell, physical strength easily reduces in the fuel cell running process, and film is fragile.If surpass 100 μ m, when then using it for fuel cell, membrane resistance is big, can not bring into play sufficient initial stage characteristic.
In this specification sheets, above-mentioned " initial stage characteristic " refers to the numerical values recited of voltage and the power generation performance under the high current density etc., and these values are to use polymer electrolyte of the present invention to carry out fuel cell running, measures the value that current density-voltage curve obtains.
Be limited to 10 μ m under the thickness of the film of above-mentioned polyelectrolyte membrane is preferred, be limited to 75 μ m on preferred.
Can obtain the polyelectrolyte membrane of the invention described above by carrying out moulding and hydrolysis.
For above-mentioned moulding, (1) can be shaped to stable fluoropolymer of the present invention membranaceous; (2) can be shaped to the fluoropolymer that contains the sulfonic acid deriveding group membranaceous without above-mentioned fluoridation.When carrying out the forming processes of above-mentioned (2), can after moulding, carry out above-mentioned fluoridation.
For example, can carry out above-mentioned moulding by melt molding methods such as the T die head method of forming, blow molding method, rolling-molding methods.
For above-mentioned moulding, in the fluoropolymer that contains the sulfonic acid deriveding group in the stable fluoropolymer in the moulding of above-mentioned (1) or the moulding of above-mentioned (2), can mix the 3rd composition according to necessity.
Can be corresponding to the method for carrying out moulding etc., suitably set the condition of above-mentioned moulding, for example, when utilizing the melt molding method of being undertaken by the T die head, molten resin temperature is preferably 100 ℃～400 ℃, more preferably 200 ℃～300 ℃.
As long as above-mentioned water decomposition is carried out after carrying out above-mentioned fluoridation, promptly can before moulding, carry out above-mentioned water decomposition, also can after moulding, carry out above-mentioned water decomposition.
In the above-mentioned water decomposition, stable fluoropolymer of the present invention is contacted with highly basic such as the NaOH aqueous solution, the KOH aqueous solution, alkalize, for example general-SO
2F is transformed to-SO
3Na ,-SO
3Metal-salt or general-COOCH such as K
3Be transformed to-COONa ,-metal-salts such as COOK etc., after washing then, further with acid solvent effects such as nitric acid, sulfuric acid, hydrochloric acid (in view of the above, for example, general-SO
2Na is transformed to-SO
3H, or general-COONa be transformed to-COOH), again by washing, can be with at above-mentioned general formula (I) or the sour deriveding group of representing by A (II), particularly-SO
2X is transformed to sulfonic acid group, according to aforesaid method, can obtain polyelectrolyte membrane.
In addition, as above-mentioned (1) stable fluoropolymer of the present invention is shaped to membranaceous method, can also enumerate following method: casting film potting syrup on supporter forms liquid state and films on supporter, then, the method (casting) of filming and removing liquid medium from liquid state.
Can followingly obtain the film potting syrup: make appropriate solvent such as water, alkanol, organic solvent, use autoclave according to necessity, 80 ℃～300 ℃ with the following polymer dispersed that obtains or be dissolved in the above-mentioned solvent, obtain the film potting syrup with this.Described polymkeric substance obtains by following operation: after the fluoropolymer that contains the sulfonic acid deriveding group through above-mentioned fluoridation being contacted with highly basic such as the NaOH aqueous solution, KOH solution alkalize and washing, further with acid solvent effects such as nitric acid, sulfuric acid, hydrochloric acid, further washing makes the sour deriveding group of side chain terminal be transformed to sulfonic acid group then.In addition, when carrying out the dispersing or dissolving of above-mentioned polymkeric substance,, can mix the 3rd composition except above-mentioned polymkeric substance according to necessity.
As the method that the film potting syrup is poured on the supporter, can make photogravure roller coat, natural roller coat, reverse known coating processes such as roller coat, scraper coating, dip-coating, airblade coating.
The supporter that uses during for cast does not limit especially, preferably uses substrates such as general polymeric film, tinsel, aluminum oxide, Si etc.When forming film/assembly of electrode (aftermentioned),, can remove this supporter from polyelectrolyte membrane according to expectation.
In addition, can remove liquid medium manufacturing and contain the polyelectrolyte membrane that strengthens body (this porous film) by after making the film potting syrup flood the porous film of special fair 5-75835 communique record; Described porous film is by carrying out prolonged treatment obtaining to poly tetrafluoroethylene [PTFE]. in addition, after in the film potting syrup, adding the fibrillation fiber that forms by PTFE, pour into a mould, remove liquid medium then, make thus as the spy and open the fibre-reinforced polyelectrolyte membrane of usefulness fibrillation shown in clear 53-149881 communique and the special public clear 63-61337 communique.
For polyelectrolyte membrane of the present invention, according to expectation, can 40 ℃～300 ℃, preferably carry out heat treated (softening) and obtain at 80 ℃～220 ℃.Further, in order to bring into play ion-exchange capacity originally fully,, can carry out acid treatment with hydrochloric acid, nitric acid etc. according to expectation.In addition, can be by using horizontal 1 tenter machine that stretch orientation is provided one by one or using 2 tenter machines to provide simultaneously and extend orientation.
In solid macromolecular electrolyte type fuel cell described later, the hydrolyzate of the fluoropolymer of aforementioned stable can be used as the film and/or the electrode of formation film/assembly of electrode.
For the film/assembly of electrode that constitutes solid macromolecular electrolyte type fuel cell, can be film be made of and electrode is not the hydrolyzate of the fluoropolymer of aforementioned stable, also can be that film is not that hydrolyzate by the fluoropolymer of aforementioned stable constitutes and electrode is, can also be film and electrode be made of the hydrolyzate of the fluoropolymer of aforementioned stable.
Active substance fixed body of the present invention contains the hydrolyzate and the active substance of the fluoropolymer of aforementioned stable.
Above-mentioned active substance fixed body normally obtains on the base material by fluid composition is coated on, and described fluid composition is dispersed with the hydrolyzate and the active substance of the fluoropolymer of aforementioned stable in liquid medium; But when being coated on the above-mentioned fluid composition that contains stable fluoropolymer and active substance on the base material, usually, can after this coating, stable fluoropolymer hydrolysis be obtained above-mentioned active fixed body.
As above-mentioned active substance, get final product so long as in above-mentioned active substance fixed body, have active active substance, do not limit especially, purpose corresponding to active substance fixed body of the present invention, suitably select active substance, for example, can use catalyzer as above-mentioned active substance sometimes suitably.Use the of the present invention active substance fixed body of catalyzer as above-mentioned active substance, can be suitably as the electrode that constitutes film/assembly of electrode in the fuel cell.
As above-mentioned catalyzer, the preferred electrode catalyzer more preferably contains the metal of platinum.
As above-mentioned catalyzer, get final product so long as be used as the catalyzer of electrode catalyst usually, do not limit especially, for example can enumerate, contain metals such as platinum, ruthenium; Organic metal chelate complexs etc., described organic metal chelate complex are the organic metal chelate complexs that has the central metal that is formed by at least a kind of metal usually, and at least a kind of its central metal is platinum or ruthenium.
As the above-mentioned metal that contains platinum, ruthenium etc., can be the metal that contains ruthenium, for example can be ruthenium simple substance etc., but preferably contain the metal of platinum.As the above-mentioned metal that contains platinum, do not limit especially, for example can enumerate the simple substance of platinum (platinum black); Platinum-ruthenium alloy etc.
Usually can be on carriers such as silica, aluminum oxide, carbon with above-mentioned catalyst cupport.
When the particle of the hydrolyzate of the fluoropolymer that requires to contain aforementioned stable or solution have well when dispersed,, except water, can also enumerate alkanols such as methyl alcohol as above-mentioned liquid medium; N-Methyl pyrrolidone nitrogen-containing solvents such as [NMP]; Ketones such as acetone; Ester classes such as ethyl acetate; Diglyme, tetrahydrofuran (THF) [THF] isopolarity ethers; Carbonates such as divinyl carbonate etc. have the polar organic solvent, and wherein, above-mentioned substance can use a kind or at least 2 kinds to mix use.
Above-mentioned fluid composition contains fluoropolymer or its hydrolyzate of aforementioned stable at least, also contains above-mentioned active substance, can also contain other composition according to necessity.
As above-mentioned other composition, for example can enumerate, be in by cast system film, impregnating and be shaped to membranaceous purpose, can enumerate the alkanols that is used to improve levelling property, be used to improve the polyoxyethylene of making film etc.
As above-mentioned base material, do not limit especially, for example can enumerate, porousness supporter, resin-formed body, metal sheet etc. are preferred for the dielectric film, porous carbon electrode of fuel cell etc.
As above-mentioned dielectric film, preferably the fluorine resin by ordinary meaning constitutes, also can be that hydrolyzate by stable fluoropolymer of the present invention constitutes. as long as in the scope of the character that does not hinder the active substance fixed body, above-mentioned dielectric film can also contain the material except the hydrolyzate of the fluorine resin of common meaning and stable fluoropolymer.
Above-mentioned " fluid composition is coated on the base material " comprises, above-mentioned fluid composition is coated on the above-mentioned base material, carry out drying according to necessity, further be transformed to hydrolyzate according to necessity, usually, further under temperature, heat more than or equal to the fusing point of the hydrolyzate of stable fluoropolymer.
As long as the condition of above-mentioned heating can be fixed on the hydrolyzate and the active substance of stable fluoropolymer on the base material, do not limit especially, for example, preferably heated several minutes for example 2 minutes～30 minutes down at 200 ℃～350 ℃.
As active substance fixed body of the present invention, during used as polymer electrolyte fuel cell, preferably contain the electrode (being also referred to as " catalyst layer ") of hydrolyzate, carbon and the catalyzer (Pt etc.) of the fluoropolymer of aforementioned stable.
Film/assembly of electrode of the present invention is the film/assembly of electrode that is formed by polyelectrolyte membrane and electrode, and it is the film/assembly of electrode that satisfies at least 1 condition that is selected from the group that is formed by following condition (1) and condition (2); Described condition (1) is: above-mentioned polyelectrolyte membrane is a polyelectrolyte membrane of the present invention; Described condition (2) is: above-mentioned electrode is above-mentioned active substance fixed body.
Film/conjugant of the present invention for example can be used for polymer electrolyte fuel cell.
When polyelectrolyte membrane of the present invention is used for polymer electrolyte fuel cell, can be used as film/assembly of electrode (membrane/electrode assembly) (hereinafter often being called " MEA "), described MEA remains on polyelectrolyte membrane sealing of the present invention between anode and the negative electrode and forms.Wherein, anode contains anode catalyst layer, has proton-conducting, and negative electrode contains cathode catalyst layer, has proton-conducting.In addition, will on the outer surface separately of anode catalyst layer and cathode catalyst layer, engage the film/assembly of electrode that gas diffusion layers (aftermentioned) is arranged and form and be also referred to as MEA.
Above-mentioned anode catalyst layer comprises and fuel (for example hydrogen) is carried out oxidation and is easy to generate the catalyzer of proton, and cathode catalyst layer comprises the catalyzer that makes proton and electronics and oxygenant (for example oxygen and air) water generation reaction.For any one of anode and negative electrode, as catalyzer, preferably use platinum or contain platinum and the alloy of ruthenium etc., the preferred catalyst particle is 10 dusts～1000 dusts.In addition, this catalyst particle preferred negative is stated from the electroconductive particle of 0.01 μ m～10 μ m sizes such as stove China ink, thermally oxidized black, Shawinigan black, carbon black, activated carbon, graphite.Catalyst particle is preferably 0.001 milligram/cm with respect to the charge capacity of catalyzer shadow area
2～10 milligrams/cm
2
Further, anode catalyst layer and cathode catalyst layer preferably contain the hydrolyzate of the fluoropolymer that the perhalogeno vinyl ether that contains sour deriveding group of above-mentioned general formula (II) expression and tetrafluoroethylene obtain through polymerization.Charge capacity with respect to the hydrolyzate of the above-mentioned perfluorocarbon sulfonic acid polymer of catalyst layer shadow area is preferably 0.001 milligram/cm
2～10 milligrams/cm
2
As the manufacture method of MEA, can enumerate for example following method.At first, the hydrolyzate of stable fluoropolymer is dissolved in the mixing solutions of alkane alcohol and water, disperses commercially available platinum load carbon (for example, the Tanaka of Japan precious metal (strain) society system TEC10E40E) to become pulpous state then therein as catalyzer.On a certain amount of one side separately of above-mentioned pulpous state liquid being coated 2 PTFE sheets, carry out drying then, form catalyst layer.Then, make the coated face of every PTFE sheet relative, between it, put into polyelectrolyte membrane of the present invention, under 100 ℃～200 ℃ by after adding hot extrusion and coming transcription to engage, by removing the PTFE sheet, obtain MEA.For the those skilled in the art, the manufacture method of MEA is known.For example, at JOURNAL OF APPLIEDELECTROCHEMISTRY, 22 (1992) p.1-7 in write up the manufacture method of MEA.
As gas diffusion layers, can use commercially available carbon cloth or carbon tissue.As the former representation example, can enumerate the system carbon cloth E-tek of U.S. DE NORA NORTH AMERICA society, B-1, representation example as the latter, can enumerate CARBEL (registered trademark, the ジ ヤ パ Application go ア テ Star Network ス of Japan (strain)), the DongレShe of Japan makes TGP-H, U.S. SPCTRACORP society system carbon tissue 2050 etc.
In addition, with electrode catalyst layer and gas diffusion layers integrated structure be called " gas diffusion electrode ".Also gas diffusion electrode can be engaged with polyelectrolyte membrane of the present invention and obtain MEA.As the representation example of commercially available gas diffusion electrode, can enumerate the system gas diffusion electrode ELAT (registered trademark) of U.S. DE NORANORTH AMERICA society (using carbon cloth) as gas diffusion layers.
Polymer electrolyte fuel cell of the present invention has above-mentioned film/assembly of electrode.
As long as above-mentioned solid macromolecular electrolyte type fuel cell has above-mentioned film/assembly of electrode, do not limit especially, usually, can contain constituents such as the electrode that constitutes solid macromolecular electrolyte type fuel cell, gas.
As mentioned above, the stable fluoropolymer of the present invention and the chemical stability excellence of hydrolyzate thereof are so can be used as the working conditions dielectric film and the material thereof of harsh fuel cells such as solid macromolecular electrolyte type fuel cell usually for a long time suitably.
By carrying out film that above-mentioned cast system film obtains, being formed at the hydrolyzate that film, active substance fixed body, polyelectrolyte membrane or solid macromolecular electrolyte type fuel cell on the porousness supporter all used stable fluoropolymer.Above-mentioned fluid composition preferably contains the hydrolyzate of stable fluoropolymer.
Polyelectrolyte membrane of the present invention except purposes as the film material of above-mentioned solid macromolecular electrolyte type fuel cell, for example can also be as lithium cell with film, salt electrolysis with film, water electrolysis with film, the electrolysis of halogenation hydracid with film, oxygen concentrator with film, humidity sensor with film, gas sensor film material with dielectric film such as film, separatory membrane or ion-exchange membrane.
The invention effect
The manufacture method of stable fluoropolymer of the present invention can fully be fluoridized the unstable group that contains the fluoropolymer of sulfonic acid deriveding group.
As mentioned above, the chemical stability excellence of stable fluoropolymer of the present invention, so its hydrolyzate can be suitably as the film material or the electrode of the dielectric film of the fuel cell of the harsh usually solid macromolecular electrolyte type fuel cell of working conditions etc. etc., thereby can obtain fuel cell membranes that fluorion is few, weather resistance is high or electrode in the draining.
Though hereinafter enumerate embodiment the present invention is further elaborated, the invention is not restricted to these embodiment.
Measuring method
1. determination of moisture method
Use moisture gasification installation (trade(brand)name: ADP-351, capital of a country electronic industry society system), as carrier gas, heated sample captures the moisture that gasifies with karl Fischer formula moisture meter, carries out coulometric titration, measures water content with drying nitrogen.
Sample size is 1 gram, and measuring temperature is 150 ℃.
Based on IR to quantification of functional group
Polymer samples was added hot extrusion 20 minutes under 270 ℃, the condition of 10MPa, making thickness is the film of 150 μ m～200 μ m, uses the FT-IR optical splitter to carry out collection of illustrative plates and measures.
3. based on the stability test of fenton reagent
(1) fenton handles 1
Polymer samples is added hot extrusion after 20 minutes under 270 ℃, the condition of 10MPa, make the end group of polymer lateral chain be transformed to sulfonic acid group, make the stability test film.
FeSO with 1 milligram
47H
2After O is dissolved in the 30 quality % aqueous hydrogen peroxide solutions of 20ml, add in the bottle of tetrafluoroethylene/perfluoro (alkyl vinyl ether) multipolymer system, and flood therein 3 the gram the stability test films, kept 20 hours at 85 ℃. then, take out the stability test film after being cooled to room temperature, use fluorine ionometer (the system Expandable ion AnalyzerEA940 of ORION society) to measure the concentration of the fluorion of liquid phase.
(2) fenton handles 2
Film liquor ratio [b/a] with 3.2 is immersed in the polyelectrolyte membrane of b gram in the aqueous hydrogen peroxide solution of a liter, the initial stage concentration that the cationic initial stage concentration of iron in the described aqueous hydrogen peroxide solution (II) is 2ppm and hydrogen peroxide is 1 quality %, 80 ℃ keep 2 hours after, take out sample polymer (above-mentioned polyelectrolyte membrane), after measuring liquid measure, with suitable chromatography of ions distilled water diluting, utilize ion-chromatographic determination fluoride ion F
-Amount.Determinator is the IC-2001 of Japan's east ソ one society's system, and the TSKgel SuperIC-Anion that uses Japan's east ソ one society's system is as the anion analysis pillar.Fluoride ion amount with the quality representation stripping of the fluoride ion of the sample polymer stripping of per 100 mass parts.
4. the measuring method of ion-exchange equivalent weight Ew
The polyelectrolyte membrane that is cut into 0.1 gram be impregnated under 25 ℃ temperature in the saturated NaCl aqueous solution of 30ml, stir down and place after 30 minutes, with phenolphthalein as indicator, (Dongxing chemistry institute society of Japan system: value TPX-90) is shown as the point of value of 6.95～7.05 scope as stoichiometric point, uses the 0.01N aqueous sodium hydroxide solution to carry out neutralization titration with PH meter.After the Na type dielectric film that obtains is rinsed well after the neutralization, carry out weighing after the vacuum-drying.With in and the time needed sodium hydroxide equivalent be made as M (mmol), the weight of Na type dielectric film is made as W (milligram), try to achieve ion-exchange equivalent weight Ew (g/eq) by following formula.
Ew＝(W/M)-22
5.
19F solid-state nuclear magnetic resonance measuring method
Carry out under the following conditions
19The F solid NMR is measured.It should be noted that in the NMR developmental tube sample be impregnated in the swelling solvent, carry out NMR in this state and measure.
Device: the German Bruker Biospin system DSX400 of society
MAS rotation number: 4.8kHz
Observing frequency: 376.5MHz
Chemical shift benchmark: CF
3COOH (77ppm)
Swelling solvent: N-methylacetamide
Measure temperature: 474K
Method of calculation are as follows.-the 79.7ppm place detects main chain end-CF
3Base (among Fig. 1 a).With this integrated intensity as A.On the other hand ,-the 76.4ppm place detects the-CF adjacent with ether of side chain
2The signal of-(b among Fig. 2).With this integrated intensity as B.Can be by above-mentioned A and B and the Ew that utilizes the sample that the measuring method of ion-exchange equivalent weight Ew of above-mentioned 4. records tries to achieve, use following formula (III) to calculate per 100,000 and constitute the terminal CF of the main chain that exists in the carbon atom of these main chains
3The number of group (X);
X＝100000/[{(B/A)×3/2}×{2×(Ew-178-50×m)/100}+2] (III)
Wherein, m defers to the value of the m of above-mentioned general formula (II) record.
6. the evaluation of fuel cell
Following the carrying out of evaluation to the fuel cell of polyelectrolyte membrane. at first, manufacturing electrode catalyst layer as described below. carbon (the system TEC10E40E of the Tanaka of Japan precious metal (strain) society of Pt is arranged with respect to the load of 1.00 grams, Pt is 36.4wt%), the fluoropolymer of 5 quality % is made solvent composition (mass ratio) is: the solution of ethanol/water=50/50, add the polymers soln of the simmer down to 11 quality % of 3.31 grams again, after further adding the ethanol of 3.24 grams, use the homogenizer thorough mixing, obtain electrode ink. this electrode ink is coated on the PTFE sheet with silk screen print method. glue spread is divided into 2 kinds, is respectively to make Pt charge capacity and polymkeric substance charge capacity be 0.15 milligram/cm
2Glue spread and make Pt charge capacity and polymkeric substance charge capacity be 0.30 milligram/cm
2After the coating, by at room temperature dry 1 hour, in air 120 ℃ obtained the electrode catalyst layer that thickness is 10 μ m down in dry 1 hour.In these electrode catalyst layers, Pt charge capacity and polymkeric substance charge capacity are 0.15 milligram/cm
2Electrode catalyst layer as anode catalyst layer, Pt charge capacity and polymkeric substance charge capacity are 0.30 milligram/cm
2Electrode catalyst layer as cathode catalyst layer.
Make the anode catalyst layer that so obtains relative with cathod catalyst, polyelectrolyte membrane is put into therebetween, add hot extrusion by pressing under the condition of 0.1MPa, with anode catalyst layer and cathode catalyst layer transcription, join on the polyelectrolyte membrane, thereby make MEA at 160 ℃, face.
Go up installation carbon cloth (system gas diffusion electrode ELAT (registered trademark) B-1 of U.S. DE NORA NORTH AMERICA society) in the both sides of this MEA (outside surface of anode catalyst layer and cathode catalyst layer) and, be assembled into evaluation electricity pool as gas diffusion layers.This evaluation electricity pool is installed on evaluating apparatus (Dongyang テ Network ニ カ society of Japan's (strain) system fuel cell evaluation system 890CL), be warming up to 80 ℃ after, at logical 150cc/ minute hydrogen of anode one side, at logical 400cc/ minute air of negative electrode one side.For gas humidification, make water bubbling mode, with hydrogen at 80 ℃, air at 50 ℃ of following humidifications to the battery condition of supplying, measure current density-voltage curve and study the initial stage characteristic.
After the research initial stage characteristic, be to carry out endurance test under 100 ℃ at battery temperature.Under arbitrary situation, make the gas humidification temperature of anode, negative electrode all be 60 ℃.When battery temperature is 100 ℃,,,, be 0.3A/cm with the current density at the state of pressurization at logical 102cc/ minute air of negative electrode one side at logical 74cc/ minute hydrogen of anode one side
2Generate electricity; In the described pressurized state, being 0.30MPa (absolute pressure) in anode one side, is 0.15MPa (absolute pressure) in negative electrode one side.At this moment, if the polymkeric substance in film or the electrode is aging, then the fluorinion concentration in the draining of anode one side and negative electrode one side increases, so use the model 9609BNionplus fluorine combined electrode (メ デ イ ト リ ア Le society of Japan system) of desktop type pH ionometer model 920Aplus to measure the fluorinion concentration in the draining for a long time.In endurance test, if generate pin hole on polyelectrolyte membrane, the phenomenon of hydrogen in a large amount of seepages of negative electrode one side then can take place, this phenomenon is called as the phenomenon of crossover leakage.In order to study the amount of this crossover leakage, measure the hydrogen concentration in the cathode side exhaust with micro GC (the system CP4900 of Dutch state Varian society), with this measured value during more than or equal to 10 times of initial stage as test endpoint.
7. the measuring method of melt index [MI]
For the mensuration of MI, according to JIS K 7210, be under 2.16 kilograms the condition at 270 ℃, load, use the system MELT IDEXER TYPE C-5059D of Japan Japan smart machine society to measure.The weight of showing the polymkeric substance of extruding with per 10 minutes gram numerical table.
Embodiment 1
(1) polymkeric substance is synthetic
At volume is in the stainless steel stirred autoclave of 3000ml, adds 300 grams and contains C
7F
15COONH
4Be the pure water of 10% the aqueous solution and 1170 grams, vacuumize, carry out nitrogen replacement fully.After autoclave vacuumized fully, importing tetrafluoroethylene [TFE] gas to gauge pressure was 0.2MPa, is warming up to 50 ℃.Then, inject the CF of 100 grams
2=CFOCF
2CF
2SO
2F imports TFE gas, and boosting to gauge pressure is 0.7MPa.Then be infused in the aqueous solution that is dissolved with 0.5 gram ammonium persulphate [APS] in the 60 gram pure water, initiated polymerization.In order to replenish the TFE that consumes owing to polymerization, supply with TFE continuously, make the pressure of autoclave remain on 0.7MPa.And supply with CF continuously
2=CFOCF
2CF
2SO
2F, by quality ratio, its feed rate is 0.53 times of the TFE that supplied with.Continue to carry out polymerization with this.
When the TFE that supplies with is 522 grams, open the pressure of autoclave, stop polymerization.Then, be cooled to room temperature, obtaining 2450 grams has the turbid water dispersion slightly, and it contains the SO that has of the 33 quality % that have an appointment
2The fluorinated polymer excessively of F.
With the above-mentioned aqueous dispersion of nitric acid condensation, wash, 90 ℃ dry 24 hours down, further 120 ℃ dry 12 hours down, obtain the fluoropolymer A of 800 grams.
Then, the 1 gram fluoropolymer A that obtains is directly joined in the tube furnace that is heated to 150 ℃, make moisture evaporation, and with drying nitrogen as carrier gas, evaporable moisture is imported to karl Fischer moisture determination device measure amount of moisture, in mass, amount of moisture is 200ppm.
In addition, the result who measures by the high temperature NMR under 300 ℃ as can be known, the CF among the fluoropolymer A
2=CFOCF
2CF
2SO
2The unitary content of F is 19 moles of %.
Above-mentioned fluoropolymer A is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 170 μ m.
The result who is measured by IR does not observe the peak that derives from sulfonic acid as can be known.In addition, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] be 0.23.
(2) fluoridize
At volume is in the autoclave (Haast Lip river Yin's nickle-base corrosion-resisting refractory alloy system) of 1000ml, and the moisture content that adds 200 grams is the above-mentioned fluoropolymer A of 200ppm, is warming up to 120 ℃ while carry out vacuum outgas.Repeat to vacuumize, behind the nitrogen replacement 3 times, importing nitrogen to gauge pressure is 0MPa.Then importing gaseous fluorinating agent, to make gauge pressure be 0.1MPa, kept 30 minutes.Described gaseous fluorinating agent is by obtaining diluted fluorine gas with nitrogen to 20 volume %.
Then, the fluorine in the autoclave is discharged, after vacuumizing, it is 0.1MPa that the importing gaseous fluorinating agent makes gauge pressure, keeps 3 hours.Described gaseous fluorinating agent is by obtaining diluted fluorine gas with nitrogen to 20 volume %.
Then, be cooled to room temperature, the fluorine in the autoclave is discharged, repeat to vacuumize, behind the nitrogen replacement 3 times, open autoclave, obtain stable fluoropolymer B.
Above-mentioned fluoropolymer B is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 170 μ m.
The result who is measured by IR does not observe the peak that derives from sulfonic acid as can be known.In addition, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] be 0.03.
With melt index meter [MI meter], the stable fluoropolymer that obtains is applied 5 kilograms load under 270 ℃, push and obtain twist yarn (strand).After the twist yarn that obtains repeated extrusion operation 2 times with the MI meter once more, twist yarn was painted hardly.
Comparative example 1
The fluoropolymer A that utilizes embodiment 1 to obtain was placed in air 2 days, and the water content that records is 700ppm.
Similarly to Example 1 this polymkeric substance is fluoridized, obtained fluoropolymer C.The top variable color of the autoclave of the fluoropolymer C that is used to obtain proves corrosion has taken place for green.
The fluoropolymer C that obtains is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 160 μ m.
The result who is measured by IR derives from the peak [z] of sulfonic acid and derives from-CF as can be known
2-the strength ratio [z/y] at peak [y] be 0.03.In addition, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] be 0.14.
With melt index meter [MI meter], the stable fluoropolymer C that obtains under 270 ℃, is applied 5 kilograms load, extrude, obtain twist yarn.After the twist yarn that obtains repeated to extrude operation 2 times with the MI meter, twist yarn was colored as dense dark brown.
By above-mentioned result as can be known, be that the comparative example 1 of 700ppm is compared with water content, water content is carried out fluorizated embodiment 1 smaller or equal to the fluoropolymer A of 500ppm can make terminal stablely, can suppress the painted of fluoropolymer in addition
Embodiment 2
The film that will obtain by embodiment 1 (2) in 20% aqueous sodium hydroxide solution, 90 ℃ handle 24 hours down after, wash, then in 6 centinormal 1 sulfuric acid, handled 24 hours in 60 ℃.Then, be washed to washings, obtain the film of sulfonic acid type for neutral.
This film after 110 ℃ of following thorough dryings, is got 3 grams, handle 1 by fenton and carry out stability test, as seen from the experiment, fluorinion concentration is 5ppm.
Comparative example 2
Use is with CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2The polymeric film that F aggregates into (trade(brand)name: Nafion 117, E.I.Du Pont Company's system) is handled 1 by fenton similarly to Example 2 and is carried out stability test as containing the sulfonic acid group fluoropolymer, and as seen from the experiment, fluorinion concentration is 20ppm.
By the aforementioned stable test-results as can be known, with CF
2=CFOCF
2CF
2SO
2After F and TFE copolymerization obtain multipolymer, further make the polymkeric substance after its end is stablized, with use CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2The polymer phase ratio of F, the former excellent in stability.
Embodiment 3
(1) polymkeric substance is synthetic
To volume is after the stainless steel stirred autoclave of 3000ml vacuumizes fully, carries out nitrogen replacement, autoclave to be vacuumized fully, adds 1530 gram perflexanes and 990 gram CF
2=CFOCF
2CF
2SO
2F transfers to 25 ℃ with temperature.To wherein importing tetrafluoroethylene [TFE] gas to gauge pressure is 0.30MPa, then is pressed into 13.14 grams and contains 10 quality % polymerization starter (C
3F
7COO)
2Perflexane solution, initiated polymerization.
In order to replenish the TFE that polymerization consumes, supply with TFE continuously, make the pressure of autoclave remain on 0.30MPa.Supply with CF discontinuously
2=CFOCF
2CF
2SO
2F amounts to 47 grams, continues to carry out polymerization.
When the TFE that supplies with is 73 grams, open the pressure of autoclave, stop polymerization.
After polyreaction finishes, drop into the chloroform of 1500ml, stirred 10 minutes.Then, use centrifuge separator to carry out solid-liquid separation, in its solids component, drop into the chloroform of 1500ml, stirred 10 minutes.Carry out this operation 3 times, washing copolymer.Then, this washing copolymer is placed under 120 ℃, vacuum, remove residual chloroform, obtain 128 gram fluoropolymer D.
Then, the 1 gram fluoropolymer D that obtains is directly joined in the tube furnace that is heated to 150 ℃, makes moisture evaporation, and with drying nitrogen as carrier gas, import to the amount that karl Fischer moisture determination device is measured moisture, in mass, the result is 50ppm.
In addition, the result who measures by the high temperature NMR under 300 ℃ as can be known, the CF among the fluoropolymer C
2=CFOCF
2CF
2SO
2The unitary content of F is 18 moles of %.
Above-mentioned fluoropolymer D is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 160 μ m.
The result who is measured by IR does not observe the peak that derives from sulfonic acid as can be known.In addition, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] be 0.08.
(2) fluoridize
100 gram fluoropolymer D are carried out the processing identical with embodiment 1, obtain stable fluoropolymer E.
Implement the add hot extrusion identical with embodiment 1 and make film, the result who is measured by IR does not observe peak that derives from sulfonic acid and the peak that derives from carboxyl as can be known.
Embodiment 4
The film of stable fluoropolymer E is carried out the processing identical with embodiment 2, obtain the film of sulfonic acid type.
This film after 110 ℃ of following thorough dryings, is got 3 grams, handle 1 by fenton and carry out stability test, as seen from the experiment, fluorinion concentration is 5ppm.
Embodiment 5
(1) polymkeric substance is synthetic
At volume is in the stainless steel stirred autoclave of 6L, adds 150 grams and contains 10% C
7F
15COONH
4The aqueous solution and 2840 the gram pure water, vacuumize, carry out nitrogen replacement fully.After autoclave vacuumized fully, importing tetrafluoroethylene [TFE] gas to gauge pressure was 0.2MPa, is warming up to 50 ℃.Then, inject 180 gram CF
2=CFOCF
2CF
2SO
2F imports TFE gas, and boosting to gauge pressure is 0.7MPa.Then be infused in the aqueous solution that is dissolved with 1.5 gram ammonium persulphates [APS] in the 20 gram pure water, initiated polymerization.
In order to replenish the TFE that polymerization consumes, supply with TFE continuously, make the pressure of autoclave remain on 0.7MPa.Further supply with CF continuously
2=CFOCF
2CF
2SO
2F continues to carry out polymerization, by quality ratio, and CF
2=CFOCF
2CF
2SO
2The feed rate of F is 0.70 times of the TFE that supplies with.
When the TFE that supplies with is 920 grams, open the pressure of autoclave, stop polymerization.Then, be cooled to room temperature, obtaining 4650 grams has the turbid water dispersion slightly, and it contains the SO that has of the 32 quality % that have an appointment
2The fluorinated polymer excessively of F.
With the above-mentioned aqueous dispersion of nitric acid condensation, wash, 90 ℃ dry 24 hours down, and further 120 ℃ dry 12 hours down, obtain 1500 gram fluoropolymer F.
Then, the 1 gram fluoropolymer F that obtains is directly joined in the tube furnace that is heated to 150 ℃, make moisture evaporation, as carrier gas, import to the amount that karl Fischer moisture determination device is measured moisture with drying nitrogen, in mass, the result is 150ppm.
In addition, the result who measures by the high temperature NMR under 300 ℃ as can be known, the CF among the fluoropolymer F
2=CFOCF
2CF
2SO
2The unitary content of F is 18.6 moles of %.
Above-mentioned fluoropolymer F is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 170 μ m.The result who is measured by IR derives from the peak [z] of sulfonic acid and derives from-CF as can be known
2-the strength ratio [z/y] at peak [y] be 0.05.In addition, the peak [x] that derives from carboxyl with derive from-CF
2-the strength ratio [x/y] at peak [y] be 0.20.
2) fluoridize
Be in Haast Lip river Yin's nickle-base corrosion-resisting refractory alloy system autoclave of 3L then, add the above-mentioned fluoropolymer F of 700 grams, be warming up to 120 ℃ while carry out vacuum outgas at volume.After repeating to vacuumize, carry out nitrogen replacement 3 times, importing nitrogen to gauge pressure is 0.5MPa.Then importing gaseous fluorinating agent, to make gauge pressure be 0MPa, kept 30 minutes.Described gaseous fluorinating agent is by obtaining diluted fluorine gas with nitrogen to 20 volume %.
Then, the fluorine in the autoclave is discharged, after vacuumizing, it is 0MPa that the importing gaseous fluorinating agent makes gauge pressure, keeps 3 hours.Described gaseous fluorinating agent is by obtaining diluted fluorine gas with nitrogen to 20 volume %.
Then, be cooled to room temperature, the fluorine in the autoclave is discharged, repeat to vacuumize, behind the nitrogen replacement 3 times, open autoclave, obtain stable fluoropolymer G.
Above-mentioned fluoropolymer G is carried out 20 minutes the hot extrusion that adds under 270 ℃, the condition of 10MPa, obtain having the transparent film of the thickness of 170 μ m.
The result who is measured by IR does not observe peak that derives from sulfonic acid and the peak that derives from carboxyl as can be known.
The MI of this stable polymer G is 3.5 (restraining/10 minutes).Then, stable fluoropolymer G is extruded melt molding at 280 ℃, obtain the thick film of 50 μ m by utilizing the T die head.Handle this film in the same manner with embodiment 2, obtain the film of sulfonic acid type.The Ew that measures the film of this sulfonic acid type according to the measuring method of above-mentioned ion-exchange equivalent weight Ew is 720 (g/eq).In addition, according to
19B/A=302.1, the X=20.4 that F solid-state nuclear magnetic resonance measuring method is measured (m=2 in the above-mentioned general formula (II)).
Further, the film of this sulfonic acid type is carried out above-mentioned fenton handle 2, by the result as can be known, with respect to the film of 100 mass parts, fluoride ion is 3.1 * 10
-4Mass parts.
Then, use this dielectric film to make film/assembly of electrode (MEA) according to aforesaid method.At this moment, the fluoropolymer that uses in the electrode is identical with dielectric film, uses the polymkeric substance that stable fluoropolymer G is processed into sulfonic acid type.
This MEA is assembled in evaluation electricity pool, and the initial stage when measuring battery temperature and be 80 ℃ according to aforesaid method is during characteristic, for voltage (V) and current density (A/cm
2) relation, current density is 0.5A/cm
2The time voltage be 0.77V, current density is 1.0A/cm
2The time voltage be 0.68V, current density is 1.5A/cm
2The time voltage be 0.55V, can obtain very high battery performance.
In addition,, can turn round 550 hours, obtain higher weather resistance for the endurance test under 100 ℃.As follows through the fluorinion concentration in the draining after 50 hours, negative electrode one side is 0.16ppm, and anode one side is 0.23ppm.In addition, as follows through the fluorinion concentration in the draining after 400 hours, negative electrode one side is 0.22ppm, and anode one side is 0.48ppm.
Comparative example 3
For fluoropolymer F, except not carrying out fluoridation, make polymkeric substance identically, with embodiment 5 in the same manner by utilizing the T die head that this polymkeric substance is extruded melt molding at 280 ℃, obtain the thick film of 50 μ m.The MI of this fluoropolymer F is 3.5 (restraining/10 minutes).This film and embodiment 2 are handled in the same manner, obtained the film of sulfonic acid type.
The Ew that measures the film of this sulfonic acid type according to the measuring method of above-mentioned ion-exchange equivalent weight Ew is 720 (g/eq).In addition, according to
19B/A=∞, the X=0 that F solid-state nuclear magnetic resonance measuring method is measured (m=2 in the above-mentioned general formula (II)).Further, the film of this sulfonic acid type is carried out above-mentioned fenton handle 2, by the result as can be known, with respect to the film of 100 mass parts, fluoride ion is 13.3 * 10
-4Mass parts.
Then, use this dielectric film to make film/assembly of electrode (MEA) according to aforesaid method.At this moment, the fluoropolymer that uses in the electrode is identical with dielectric film, and use will not be processed into the polymkeric substance of sulfonic acid type through the fluoropolymer F of fluoridation.
This MEA is assembled in evaluation electricity pool, and the initial stage when measuring battery temperature and be 80 ℃ according to aforesaid method is during characteristic, for voltage (V) and current density (A/cm
2) relation, current density is 0.5A/cm
2The time voltage be 0.72V, current density is 1.0A/cm
2The time voltage be 0.44V, current density is 1.5A/cm
2The time battery can not turn round.
In addition, for the endurance test under 100 ℃, during through 85 hours running, because seepage causes running to finish.As follows through the fluorinion concentration in the draining after 50 hours, negative electrode one side is 2.8ppm, and anode one side is 6.1ppm.
Comparative example 4
Will by comparative example 1 obtain through fluorizated fluoropolymer C, with embodiment 5 in the same manner by utilizing the T die head to extruding melt molding at 280 ℃, obtain the thick film of 50 μ m.The MI of this fluoropolymer C is 3.2 (restraining/10 minutes).This film and embodiment 2 are handled in the same manner, obtained the film of sulfonic acid type.The Ew that measures the film of this sulfonic acid type according to the measuring method of above-mentioned ion-exchange equivalent weight Ew is 720 (g/eq).In addition, according to
19B/A=921, the X=6.7 that F solid-state nuclear magnetic resonance measuring method is measured (m=2 in the above-mentioned general formula (II)). further, the film of this sulfonic acid type is carried out above-mentioned fenton handle 2, by the result as can be known, with respect to the film of 100 mass parts, fluoride ion is 12.8 * 10
-4Mass parts.
Then, according to aforesaid method, use this dielectric film to make film/assembly of electrode (MEA).At this moment, the fluoropolymer that uses in the electrode is identical with dielectric film, uses the polymkeric substance that fluoropolymer C is processed into sulfonic acid type.
This MEA is assembled in evaluation electricity pool, and the initial stage when measuring battery temperature and be 80 ℃ according to aforesaid method is during characteristic, for voltage (V) and current density (A/cm
2) relation, current density is 0.5A/cm
2The time voltage be 0.75V, current density is 1.0A/cm
2The time voltage be 0.52V, current density is 1.5A/cm
2The time voltage be 0.18V.
In addition, for the endurance test under 100 ℃, during through 120 hours running, because seepage causes running to finish.As follows through the fluorinion concentration in the draining after 50 hours, negative electrode one side is 1.18ppm, and anode one side is 2.5ppm.
Utilizability on the industry
Utilize the manufacture method of stable fluoropolymer of the present invention, can provide the manufacturing of the film material that is adapted at using under the harsh conditions, such as electrolyte film in fuel cell etc.
As mentioned above, the chemical stability excellence of stable fluoropolymer of the present invention, so its hydrolysate can be used as service condition usually film material or the electrodes such as dielectric film of the harsh fuel cells such as solid macromolecular electrolyte type fuel cell suitably, thereby can obtain the fuel cell membranes that fluorine ion is few and durability is high or electrode in the draining.
Claims (8)
1. the manufacture method of stable fluoropolymer, it is by the process object thing that contains fluoropolymer is carried out the manufacture method that fluoridation is made stable fluoropolymer, described fluoropolymer in the described process object thing has the sulfonic acid deriveding group, it is characterized in that the described fluoropolymer that contains the sulfonic acid deriveding group is to have-SO
3The fluoropolymer of M, in the described process object thing, in mass, moisture is smaller or equal to 500ppm ,-SO
3M among the M represents H, NR
1R
2R
3R
4Or M
1 1/L, R
1, R
2, R
3And R
4Identical or different, expression H or carbonatoms are 1～4 alkyl, M
1The metal of expression L valency.
2. the manufacture method of stable fluoropolymer as claimed in claim 1, wherein, the described fluoropolymer that contains the sulfonic acid deriveding group further has-SO
2X ,-SO
2X among the X represent F, Cl, Br, I or-NR
5R
6, R
5, R
6Identical or different, expression H, alkali metal, alkyl or contain the group of alkylsulfonyl.
3. the manufacture method of stable fluoropolymer as claimed in claim 1 or 2, wherein, the described fluoropolymer that contains the sulfonic acid deriveding group further has-COOH at the polymer chain end.
4. the manufacture method of stable fluoropolymer as claimed in claim 1 or 2, wherein, described fluoridation is to use the gaseous fluorinating agent that contains the fluorine source to carry out, and described fluorine source is to be selected from by F
2, SF
4, IF
5, NF
3, PF
5, ClF and ClF
3At least a kind of material in the group that forms, described fluorine source is more than or equal to 1 volume % of described gaseous fluorinating agent.
5. the manufacture method of stable fluoropolymer as claimed in claim 4, wherein, described fluorine source is F
2
6. the manufacture method of stable fluoropolymer as claimed in claim 1 or 2, wherein, the described fluoropolymer that contains the sulfonic acid deriveding group is by the perhalogeno vinyl ether that contains sour deriveding group of following general formula (I) expression and 2 yuan or the multiple copolymer that can form with the described monomer that contains the perhalogeno vinyl ether copolymerization of sour deriveding group; Described monomer that can copolymerization is other vinyl ether and a vinyl-type monomer except the described perhalogeno vinyl ether that contains sour deriveding group; In the described multipolymer, the perhalogeno vinyl ether unit that contains sour deriveding group that the described perhalogeno vinyl ether that contains sour deriveding group forms is 5 moles of %～40 mole %, the vinyl-type monomer unit that described vinyl-type monomer forms is 60 moles of %～95 mole %, and other the vinyl ether unit that described other vinyl ether forms is 0 mole of %～5 mole %;
CF
2＝CF-O-(CF
2CFY
1-O)
n-(CFY
2)
m-A (I)
In the general formula (I), Y
1Expression F, Cl, Br, I or perfluoroalkyl, n represents 0～3 integer, n Y
1Identical or different, Y
2Expression F, Cl, Br or I, m represents 1～5 integer, when m is 2～5 integer, m Y
2Identical or different, A represents-SO
2X, X represent F, Cl, Br, I or-NR
5R
6, R
5, R
6Identical or different, expression H, alkali metal, alkyl or contain the group of alkylsulfonyl.
7. the manufacture method of stable fluoropolymer as claimed in claim 6, wherein, n is 0.
8. the manufacture method of stable fluoropolymer as claimed in claim 6, wherein, Y
2Be F, and m is 2.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003318243 | 2003-09-10 | ||
| JP318243/2003 | 2003-09-10 | ||
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| JP226891/2004 | 2004-08-03 | ||
| PCT/JP2004/013241 WO2005028522A1 (en) | 2003-09-10 | 2004-09-10 | Stabilized fluoropolymer and method for producing same |
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| KR100978609B1 (en) * | 2007-11-27 | 2010-08-27 | 한양대학교 산학협력단 | Proton exchange membrane using surface treatment technique based on direct fluorination, membrane-electrode assembly, and fuel cell comprising the same |
| US8658707B2 (en) * | 2009-03-24 | 2014-02-25 | W. L. Gore & Associates, Inc. | Expandable functional TFE copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products |
| CN105308217B (en) * | 2013-06-19 | 2018-06-12 | 旭化成株式会社 | Containing fluorine system polymer, cation-exchange membrane and electrolytic cell |
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| US5674957A (en) * | 1995-03-10 | 1997-10-07 | The University Of North Carolina At Chapel Hill | Nonaqueous polymerization of fluoromonomers |
| CN1310190A (en) * | 2000-02-15 | 2001-08-29 | 旭硝子株式会社 | Block polymer and its producing process, and the same polymer electrolytic fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348538A (en) | 2009-01-21 |
| CN101348538B (en) | 2011-10-05 |
| CN1849345A (en) | 2006-10-18 |
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